WO2014161621A1 - High stiffness polypropylene compositions - Google Patents

High stiffness polypropylene compositions Download PDF

Info

Publication number
WO2014161621A1
WO2014161621A1 PCT/EP2014/000388 EP2014000388W WO2014161621A1 WO 2014161621 A1 WO2014161621 A1 WO 2014161621A1 EP 2014000388 W EP2014000388 W EP 2014000388W WO 2014161621 A1 WO2014161621 A1 WO 2014161621A1
Authority
WO
WIPO (PCT)
Prior art keywords
preferably
polypropylene composition
heterophasic polypropylene
wt
composition according
Prior art date
Application number
PCT/EP2014/000388
Other languages
French (fr)
Inventor
Thomas Horill
Petar Doshev
Tua Sundholm
Martina Sandholzer
Klaus Bernreitner
Original Assignee
Borealis Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP13001743.7A priority Critical patent/EP2787034A1/en
Priority to EP13001743.7 priority
Application filed by Borealis Ag filed Critical Borealis Ag
Publication of WO2014161621A1 publication Critical patent/WO2014161621A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083Nucleating agents promoting the crystallisation of the polymer matrix
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00Compositions of rubber derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00Rigid pipes
    • F16L9/12Rigid pipes of plastics with or without reinforcement
    • F16L9/127Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/02Heterophasic composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/02Ziegler natta catalyst

Abstract

Heterophasic polypropylene composition comprising a propylene homo- or random copolymer matrix phase (A), and an ethylene-propylene copolymer rubber phase (B) dispersed within the matrix phase, the heterophasic polypropylene composition including a fraction soluble in pxylene at 25°C (XCS fraction) which is present in the resin in an amount of 4 to 14 wt.-%, and a fraction insoluble in p-xylene at 25 °C (XCU fraction) which is present in the resin in an amount of 86 to 96 wt.-%, wherein the heterophasic polypropylene composition has an MFR2, determined according to ISO 1133 at 230 °C and under a load of 2.16 kg, of 4.0 to 8.0 g/10 min; and wherein the heterophasic polypropylene composition has a flexural modulus higher than 1500 MPa measured on an injection moulded specimen with the dimension 80x10x4 mm3 according to ISO 178; and wherein the heterophasic polypropylene composition has a content of monomer units derived from ethylene of 2.0 to 7.0 wt.-%.

Description

High stiffness polypropylene compositions

Introduction

The present invention relates to a heterophasic polypropylene composition comprising a propylene homo- or random copolymer matrix phase and an ethylene-propylene copolymer rubber phase dispersed within the matrix phase showing excellent processability and stiffness at good impact properties. The present invention further relates to a filled heterophasic polypropylene composition and to a process for producing the heterophasic polypropylene composition and the filled heterophasic polypropylene composition as well as the use of thereof for the production of articles.

State of the art

Well-known polypropylenes of commerce are particularly isotactic, semi- crystalline, thermoplastic polymer materials with excellent cost- to performance ratio. However, their brittleness under impact loading limits the utilisation.

A well known approach for improving the toughness of an isotactic polypropylene is the incorporation of ethylene-propylene copolymer as dispersed phase into the polypropylene matrix.

Commonly, infiltration boxes that are installed in the soil are exposed to impact before and during installation and thus need sufficient impact resistance to prevent damage to the article during transportation, handling and installation. At the same time, such infiltration boxes need to withstand the high pressure of the soil once installed and thus need sufficient stiffness and high creep resistance not to be deformed and collapse under the soil load. Moreover, infiltration boxes are most easily produced by injection moulding of a polymer requiring a good processability. Thus, an appropriate polymer for the production of infiltration boxes includes a good stiffness/impact balance at good injection moulding processability, i.e. melt flow rates.

For instance, EP 1 619 217 A1 provides a heterophasic propylene polymer with good results as to softness and toughness, even though the toughness at low temperature could be still improved. Moreover the polymer, which however is appreciated under commercial aspects limiting industrial applicability.

EP 2 072 576 A1 relates to a polypropylene as well as its use. An increase in low temperature toughness was achieved by reactive modification with at least bifunctionally unsaturated compounds.

Soft heterophasic polypropylene copolymers with low tensile modulus and high comonomer content are prepared in EP 0 991 719. Heterophasic polypropylene copolymers with a tensile modulus between 200 and 340 MPa are obtained. However, the heterophasic polypropylene copolymers exhibit inferior impact properties.

WO 201 1/1 17103 A1 discloses a heterophasic polypropylene copolymer with a broad molecular weight and a dispersed ethylene-propylene rubber phase exhibiting a high intrinsic viscosity. Such a composition shows a good stiffness/impact balance. However, the processability concerning injection moulding is limited due to low melt flow rate.

Considering the above disadvantages it is an object of the present invention to overcome the above disadvantages and to provide a polypropylene resin that shows a high processability in regard of injection moulding together with excellent stiffness/impact balance.

Objective of the present invention

The present invention is based on the finding that the balance of properties is improved when a propylene homo^ or random copolymer as a matrix phase is combined with a dispersed phase comprising an ethylene- propylene copolymer rubber, whereby the heterophasic polypropylene composition has a content of monomer units derived from ethylene of 2.0 to 7.0 wt.-%.

Summary of the present invention

Hence, the present invention provides

a heterophasic polypropylene composition comprising

a propylene homo- or random copolymer matrix phase (A), and

an ethylene-propylene copolymer rubber phase (B) dispersed within the matrix phase, the heterophasic polypropylene composition including

a fraction soluble in p-xylene at 25°C (XCS fraction) which is present in the resin in an amount of 4 to 14 wt.-%, and

a fraction insoluble in p-xylene at 25 °C (XCU fraction) which is present in the resin in an amount of 86 to 96 wt.-%,

wherein the heterophasic polypropylene composition has an MFR2, determined according to ISO 1 133 at 230 °C and under a load of 2.16 kg, of 4.0 to 8.0 g/10 min; and

wherein the heterophasic polypropylene composition has a flexural modulus higher than 1500 MPa measured on an injection moulded specimen with the dimension 80x 0x4 mm3 according to ISO 178; and wherein the heterophasic polypropylene composition has a content of monomer units derived from ethylene of 2.0 to 7.0 wt.-%.

It has been surprisingly found that such heterophasic polypropylene compositions show an improved balance of processability, stiffness and constant impact properties within a certain range of temperatures.

In the following, the disclosure refers to the substances and phases as parts of the present invention as:

A propylene homo- or random copolymer matrix phase (A)

An ethylene-propylene copolymer rubber phase (B)

An inorganic filler (C)

Modifiers (D)

Additives (E)

Nucleating agent(s) (F)

Definitions

The term "heterophasic polypropylene composition" used herein denotes a heterophasic composition well known in the art including a crystalline matrix and a rubber phase dispersed therein.

The fraction soluble in p-xylene (XCS fraction) denotes the fraction of the heterophasic polypropylene composition that is soluble in p-xylene at 25 °C representing for the most part amorphous ethylene-propylene copolymer.

The fraction insoluble in p-xylene at 25 °C (XCU fraction) is meant to be the fraction of the heterophasic polypropylene composition that is not soluble in p-xylene at 25 °C representing for the most part the propylene homo or random copolymer matrix phase.

A mineral filler denotes a filler of natural origin which is at least partially crystalline.

An inorganic filler denotes a filler not containing organic compounds.

A polymerisation stage denotes a single polymerisation reactor or a sequential arrangement of polymerisation reactors realizing a product with defined properties.

A reaction step or polymerisation step denotes a single polymerisation process in exactly one polymerisation reactor.

Heterophasic polypropylene composition a) MFR2

The heterophasic polypropylene composition according to the present invention has a melt flow rate MFR2 (2.16 kg, 230 °C) of 4.0 to 8.0 g/10 min, more preferably of 4.0 to 7.0 g/10 min, even more preferably of 4.0 to 6.5 g/10 min and most preferably of 4.0 to 6.0 g/10 min, determined according to ISO 1 133. b) Comonomer content

Further, the heterophasic polypropylene composition according to the present invention has a content of monomer units derived from ethylene, butene, pentene, hexene and/or octene of 2.0 to 7.0 wt.-%, preferably 2.0 to 7.0 wt.-%, more preferably of 3.0 to 6.5 wt.-%, and most preferably of 4.0 to 5.5 wt.-%. The content of monomer units derived from ethylene, butene, pentene, hexene and/or octene also can be denoted C2-content, C4-content, Cs-content, C6-content or C8-content respectively. The preferred comonomer is ethylene. c) XCS fraction

The fraction soluble in p-xylene at 25 °C (XCS) is present in the heterophasic polypropylene composition in an amount of 4 to 14 wt.-%, preferably of 8 to 13 wt.-%, and more preferably of 10 to 12 wt.-%. d) XCU fraction

The heterophasic polypropylene composition according to the invention preferably includes a XCU fraction in an amount of 86 to 96 wt.-%, more preferably 87 to 92 wt.-%, and most preferably 88 to 90 wt.-%. e) Crystallization temperature Tc

The heterophasic polypropylene composition according to the present invention preferably has a crystallization temperature, Tc, of 1 18 to 135 °C, more preferably 128 to 132 °C, an most preferably 129 to 131 °C measured according to ISO 1 1357-1 , -2 and -3. The crystallization temperature Tc is mainly dependent on the polymer structure and insofar can be {inter alia) influenced by use of nucleating agents. For example, when a nucleating agent such as described in EP 1 028 985, Example 1 , is used, the Tc can be increased significantly. f) Heat of melting HM

The heterophasic polypropylene composition according to the present invention preferably has a heat of melting, HM, of 85 to 125 J/g, more preferably of 90 to 120 J/g, and most preferably of 95 to 1 16 J/g measured by differential scanning calorimetry (DSC according to ISO 1 1357-1 , -2, and -3. g) Heat of crystallization Hc

The heterophasic polypropylene composition according to the present invention preferably has a heat of crystallization, Hc, of 80 to 120 J/g, more preferably of 85 to 1 15 J/g, and most preferably of 90 to 1 1 1 J/g measured by differential scanning calorimetry (DSC) according to ISO 1 1357-1 , -2, and -3. h) Charpy Notched Impact Strength at 23 °C

Furthermore, the heterophasic polypropylene composition according to the invention preferably has a Charpy Notched Impact Strength (NIS) at 23 °C of above 5.5 J/m2, preferably of above 6.0 J/m2, and most preferably of above 7.0 J/m2 measured accordingly to ISO 179- eA:2000. Usually, the Charpy Notch Impact Strength (NIS) at 23 °C of the invention will not be higher than 14, frequently not higher than 12 J/m2. i) Polydispersity index PI

The heterophasic polypropylene composition according to the present invention preferably has a polydispersity index, PI, measured at 200°C of 2.5 to 6.0 Pa"1, more preferably of 2.8 to 5.0 Pa"1 , and most preferably of 3.0 to 4.2 Pa"1. j) Flexural modulus

The heterophasic polypropylene composition according to the invention has a flexural modulus of higher than 1500 MPa, preferably of higher than 1625 MPa, more preferably of higher than 1650 MPa and most preferably of higher than 1700 MPa, determined according to ISO 178. k) Modifier (D) content

The heterophasic polypropylene composition according to the present invention preferably has optionally a modifier content (D) in amount of below 10 wt.-%, more preferably below 7 wt.-%, and most preferably below 5 wt.-% with respect to the total weight of the heterophasic polypropylene composition.

I) Additive (E) content

The heterophasic polypropylene composition according to the present invention preferably has an additive content (E) in an amount of below 1.0 wt.-%, more preferably in an amount of 0.1 to 0.8 wt.-%, and most preferably in an amount of 0.2 to 0.7 wt.-% with respect to the total weight of the heterophasic polypropylene composition. m) Nucleating agents (F) content

The heterophasic polypropylene composition according to the present invention optionally has a content of nucleating agent(s) (F) of 50 ppm to 1.5 wt.-%, preferably of 100 ppm to 1.3 wt.-%, and most preferably of 0.1 to 1 .2 wt.-% with respect to the total weight of the heterophasic polypropylene composition. n) Amount of additives (E) and nucleating agents (F)

The heterophasic polypropylene composition according to the present invention preferably has a sum of the contents of nucleation agent(s) (F) and additive(s) (E) of 0.1 to 2.3 wt.-%, preferably of 0.5 to 2.1 wt.-%, and most preferably of 0.3 to 1.9 wt.-% with respect to the total weight of the heterophasic polypropylene composition. XCS phase a) Comonomer content

It is preferred that the fraction soluble in p-xylene at 25 °C (XCS) has a C2-content of 25 to 55 wt.-%, more preferably of 30 to 50 wt.-%, and most preferably of 35 to 45 wt.-%. b) Intrinsic viscosity

The XCS phase preferably has an intrinsic viscosity of 3.5 to 6.0 dl/g, more preferably of 4.0 to 5.8 dl/g, and most preferably of 4.4 to 5.5 dl/g measured in decalin at 135 °C according to DIN EN ISO 1628-1 and -3. Filled heterophasic polypropylene composition a) Mineral, inorganic filler (C) content

The present invention is further concerned with a filled heterophasic polypropylene composition consisting of the polypropylene composition as described herein and a mineral, inorganic filler (C) in an amount of 5 to 55 wt.-%, preferably 15 to 45 wt.-%, and more preferably 20 to 40 wt.-% with respect to the total weight of the filled heterophasic polypropylene composition. b) Charpy Notched Impact Strength at 23 °C

Furthermore, the filled heterophasic polypropylene composition according to the invention preferably has a Charpy Notched Impact Strength (NIS) at 23 °C of above 2.5 J/m2, preferably of above 3.0 J/m2, and most preferably of above 3.5 J/m2 measured accordingly to ISO 79-1eA:2000. Usually, the Charpy Notch Impact Strength (NIS) at 23 °C of the invention will not be higher than 14, frequently not higher than 12 J/m2. The addition of talc as a filler in comparison to the composition with talc as a nucleating agent only leads to a reduction in impact properties. c) Flexural modulus

The filled heterophasic polypropylene composition according to present invention preferably has a flexural modulus of higher than 2500 MPa, more preferably 2700 MPa and most preferably 2900 MPa determined according to ISO 178.

Matrix phase (A)

In a first embodiment the matrix phase (A) consists of at least one propylene random copolymer. When the matrix phase consists of two or more propylene random copolymers differing as to their molecular weight, the matrix will be bimodal or even multimodal.

In a second embodiment the matrix phase (A) consists of at least one propylene homopolymer. When the matrix phase consists of two or more propylene homopolymers differing as to their molecular weight, the matrix will be bimodal or even multimodal.

In a third embodiment the matrix phase (A) consists of a mixture of at least one propylene homopolymer with at least one propylene random copolymer. Again a bimodal or multimodal matrix can result. Ethylene-propylene rubber phase (B)

The ethylene-propylene copolymer rubber phase (B) may consist of a single compound, but may also comprise a mixture of different compounds. This also applies for all preferred embodiments of component (B). Mineral, inorganic filler (C)

The mineral, inorganic filler (C) is preferably selected from the group of talc, calcium carbonate, mica, kaolin, clay, and/or barium sulphate. The preferred filler is talc.

More preferably talc used for the production of the composition has an aspect ratio of 1 :1 to 100:1 , even more preferably talc with an aspect ratio of 1 :1 to 50:1 , and most preferably talc with an aspect ratio of 1 .1 to 25: 1.

Talc has a nucleating effect on polypropylene, and it should be understood that talc can be used as both a nucleating agent (F) or an inorganic filler (C). As a matter of definition, added talc up to an amount of 1.5 wt.-% always has a nucleating effect on the final composition, whereas additional amounts of talc fulfil the function of a filler. Therefore, the addition of talc will always have a nucleating effect.

Modifiers (D) may be included during the polymerisation process or after the polymerisation by melt mixing. Modifiers (D)

Suitable modifiers include other thermoplastics like polyethylene homo- or copolymers, poly-1 -butene, poly-4-methylpentene-1 and/or thermoplastic elastomers like ethylene-propylene rubber, styrene elastomers, or polypropylene impact copolymers.

It should further be mentioned that the use of modifiers (D), particularly ethylene-propylene or ethylene-butene ,or preferably ethylene-octene impact modifiers will contribute to the fraction soluble in p-xylene (XCS fraction) and may form a mixture with the ethylene propylene copolymer rubber material.

The at least one modifier is preferably a polymeric compound, more preferably an impact modifier, even more preferably an ethylene- propylene, ethylene-butene or ethylene-octene impact modifier, and most preferably a ethylene-octene impact modifier. Additives (E)

Additives (E) may be included during the polymerisation process or after the polymerisation by melt mixing.

Suitable additives include stabilizers such as UV-stabilisers, hindered amine stabilisers (HALS), process stabilisers such as phosphites, long term stabilisers such as thiosynergists and phenolic antioxidants, alkyl radical scavengers, lubricants, processing aids, pigments and foaming agents.

Nucleating agents (F)

Nucleating agent(s) (F) may optionally be included during the polymerisation process or after the polymerisation by melt mixing.

Suitable nucleating agents include alpha nucleating agents like talc, sodium benzoates, vinyl cycloalkane polymer, e.g. vinyl cyclohexane (VCH) polymer, vinyl cyclopentane polymer and vinyl-2-methyl cyclohexane polymer. The preferred nucleating agents are talc and vinylcyclohexane, even more preferred the combination of talc and vinylcyclohexane, in small amount of 50 ppm to 1 .5 wt.-%, more preferably of 100 ppm to 1 .3 wt.-%, even more preferably of 1000 ppm to 1 .2 wt.-% with respect to the total weight of the heterophasic polypropylene composition.

Process

The present invention is further concerned with a process for the provision of heterophasic polypropylene composition as described above. The present invention insofar provides

a process for producing the heterophasic polypropylene composition in the presence of a Ziegler-Natta catalytic system modified with vinyicyclohexane comprising a cocatalyst, wherein the process comprises a) production of a first material in a first polymerisation stage (I), having an MFR2 (2.16 kg, 230 °C) of 0.5 to 8 g/10 min, further having a XCS content of 0.5 to 2 wt.-%,

wherein the first polymerisation stage (I) comprises a slurry reactor and the process is run at a temperature of 70 to 95 °C and a pressure of 50 to 60 barg;

b) transferring said first material in a second polymerisation stage (II); c) further producing a second material,

wherein the second polymerisation stage (II) comprises a gas phase reactor and the process is run at a temperature of 80 to 95 °C and a pressure of 20 to 35 barg;

d) transferring the mixture of said first and second materials having a MFR2 of 6 to 8 g/10 min in a third polymerisation stage (III), wherein the third polymerisation stage (III) comprises a gas phase reactor and the process is run at a temperature of 60 to 90 °C and a pressure of 14 to 22 barg;

e) compounding the reaction product of the third polymerisation stage (III) with additive(s), optionally nucleating agent(s), optionally modifier(s) and/or optionally mineral inorganic filler(s). a) Catalytic system

The catalyst for producing the heterophasic polypropylene composition according to the present invention usually is a Ziegler-Natta catalyst. Such Ziegler Natta catalysts are described in EP 1 632 529, EP 0 491 566 A1 , EP 0 591 224 A1 , and particularly EP 1 028 985 and comprise a catalyst component, a cocatalyst component, and an external donor, whereby the catalyst component of the catalyst system primarily contains magnesium, titanium, halogen and an internal donor.

The catalyst preferably contains a transition metal compound as a procatalyst component. The transition metal compound is selected from the group of titanium compounds having an oxidation degree of 3 or 4, vanadium compounds, zirconium compounds, chromium compounds, cobalt compounds, nickel compounds, tungsten compounds and rare earthmetal compounds, titanium trichloride and titanium tetrachloride being particularly preferred. Examples of suitable catalyst systems are described in, for example, Finnish Patents Nos.86866, 96615 and 88047 and 88048.

These compounds may be supported on a particulate support, such as inorganic oxide, like silica or alumina, or, usually, the magnesium halide itself may form the solid support. Examples of such catalysts are disclosed, among others, in WO 87/07620, WO 92/21705, WO 93/1 1 165, WO 93/1 1 166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842, WO 92/19653, WO 92/19658

One particularly preferable catalyst, which can be used in the present invention, is disclosed in Fl Patent No. 88047 (WO 92/1 19653). Another preferred catalyst is disclosed in Finnish Patent Application No. 963707.

Preferably the catalyst for producing the unmodified heterophasic propylene polymer composition is a catalyst modified by a vinyl compound of the formula (I) as a nucleating agent. A catalyst modified by a vinyl compound of the formula (I) is a catalyst obtainable by mixing a vinyl compound of the formula (I) with the catalytic components.

CH2=CH-CHR1 R2 (I) Even more preferably, said nucleating agent is selected from: vinyl cycloalkane polymer, preferably vinyl cyclohexane (VCH) polymer, vinyl cyclopentane polymer and vinyl-2-methyl cyclohexane polymer. The most preferred nucleating agent is vinyl cyclohexane (VCH) polymer.

More preferably the catalyst for producing the heterophasic propylene polymer composition according to the present invention is polymerised with a vinyl compound of the formula (I) as described above, preferably with vinyl cyclohexane (VCH) polymer.

Further preferably, the weight ratio of the polymer of the vinyl compound of the formula (I) as defined above, preferably of the vinyl cyclohexyl (VCH) polymer, to solid catalyst component after the modification step is up to 5 (5: 1), preferably up to 3 (3: 1 ) most preferably is from 0.8 (1 :2) to 2 (2: 1 ). In other words a polyvinyl cyclohexyl (pVCH) modified solid Ziegler- Natta catalyst system is applied.

It is thereby preferred that the vinyl compound of formula (I) as described above is incorporated to the matrix phase (A) by polymerizing the propylene matrix phase (A) in the presence of a modified catalyst system, wherein the modification means the polymerisation of a vinyl compound of formula (I) as defined above, more preferably of vinyl cyclohexane (VCH), in the presence of said catalyst. The modification is preferably effected by polymerising a vinyl compound of the formula (I) as defined above, preferably with vinyl cyclohexane (VCH) in the presence of the solid Ziegler Natta catalyst component.

A catalyst system useful in the present process can be prepared by reacting a magnesium halide compound with a titanium compound and an internal donor.

The magnesium halide compound is, for example, selected from the group of magnesium chloride, a complex of magnesium chloride with a lower alkanol and other derivatives of magnesium chloride. MgCI2 can be used as such or it can be combined with silica, e.g. by absorbing the silica with a solution or slurry containing MgCI2. The lower alkanol used can be preferably methanol or ethanol, particularly ethanol.

The titanium compound used in the preparation of the procatalyst is preferably an organic or inorganic titanium compound, having an oxidation state of titanium of 3 or 4. Also other transition metal compounds, such as vanadium, zirconium, chromium, molybdenum and tungsten compounds can be mixed with the titanium compound. The titanium compound usually is halide or oxyhalide, an organic metal halide, or a purely metal organic compound, in which only organic ligands have been attached to the transition metal. Particularly preferable are the titanium halides, especially TiCI4. Preferably the titanation is for producing propylene homo- or copolymers.

In addition to the magnesium halide and transition metal compound the solid transition metal component usually also comprises an electron donor

(internal electron donor). Suitable electron donors are, among others, esters of carboxylic acids, like phthalates, citraconates, and succinates.

Also oxygen- or nitrogen-containing silicon compounds may be used.

Examples of catalysts with suitable compounds are shown e.g. in WO 92/19659, WO 92/19653, WO 92/19658, US 4 347 160,

US 4 382 019, US 4 435 550, US 4 465 782, US 4 473 660, US 4 530 912 and US 4 560 671.

The cocatalyst used in combination with the transition metal compound typically comprises an aluminium alkyl compound. The aluminium alkyl compound is preferably trialkyl aluminium such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium or tri-n-octylaluminium, most preferably triethylaluminium . However, it may also be an alkylaluminium halide, such as diethylaluminium chloride, dimethylaluminium chloride and ethylaluminium sesquichloride.

The external donor of the preferred catalyst may be silanes, e.g. dicyclopentyldimethoxysilane (DCPDMS), cyclohexylmethyl- dimethoxysilane (CHMDMS), diethylaminotriethoxysilane or dicyclopentyldimethoxysilane.

The ratio of the cocatalyst/donor (mol/mol) is preferably 8.0 to 10.0, more preferably 8.5 to 9.5.

Preferably, the heterophasic polymer composition is prepared in a sequential polymerisation process. The term "sequential polymerisation process" shall indicate that the heterophasic polymer composition is produced in at least two, particularly three reactors connected in series. Sequential polymerisation process such as developed by Borealis A/S, Denmark (known as BORSTAR® technology) are well known in the art and described in patent literature, such as in EP 0 887 379, WO 92/12182, WO98/58975 WO 2004/000899, WO 2004/1 1 1095, WO 99/24478, WO 99/24479 or in WO 00/68315. A further particularly suitable sequential polymerisation process is the Spheripol® process of Basel!.

In the process of the present invention, the catalyst system used may be varied between stages but is preferably the same for all stages. Thus, no additional catalyst is introduced into the second and third polymerisation stage (II) and (III).

Preferably the heterophasic polyolefin composition according to the present invention is obtained by a multistage polymerisation process, as described above, in the presence of a catalyst system comprising as one component a Ziegler-Natta procatalyst, which contains a trans- esterification product of a lower alcohol and a phthalic ester.

The procatalyst used according to the invention is preferably prepared by a) reacting a spray crystallized or emulsion solidified adduct of MgCl2 and a C1-C2 alcohol with TiC^

b) reacting the product of stage a) with a dialkylphthalate of formula (II)

Figure imgf000017_0001

wherein R1 ' and R2' are independently at least a C5 alkyl

under conditions where a transesterification between said Ci to C2 alcohol and said dialkylphthalate of formula (II) takes place to form the internal donor

c) washing the product of stage b) or

d) optionally reacting the product of step c) with additional T1CI4.

The procatalyst is produced as defined for example in the patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566. The content of these documents is herein included by reference.

Preferably the procatalyst used according to the invention contains not more than 2.5 wt-% of titanium. Its donor content is preferably between 5 to 15 wt.-%

A further component of the catalysts system used is an external donor represented by formula (Ilia) or (lllb). Formula (Ilia) is defined by

Si(OCH3)2( 3)2 (Ilia) wherein R3 represents a branched-alkyl group having 3 to 12 carbon atoms, preferably a branched-alkyl group having 3 to 6 carbon atoms, or a cyclo-alkyl having 4 to 12 carbon atoms, preferably a cyclo-alkyl having 5 to 8 carbon atoms.

It is in particular preferred that R is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert. -butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

Formula (lllb) is defined by

Si(OCH2CH3)3(NRxRy) (lllb) wherein Rx and Ry can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.

Rx and Ry are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. It is in particular preferred that Rx and Ry are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert.-butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

More preferably both Rx and Ry are the same, yet more preferably both Rx and Ry are an ethyl group.

More preferably the external donor of formula (lllb) is diethylaminotriethoxysilane. Most preferably the external donor is of formula (Ilia), like dicyclopentyl dimethoxy silane [Si(OCH3)2(cyclo-pentyl)2] or diisopropyl dimethoxy silane [Si(OCH3)2(CH(CH3)2)2].

The present invention also pertains to a heterophasic polypropylene composition obtainable according to the process as described herein (above and in the following). b) General process

The present invention further relates to a process for producing the heterophasic polypropylene according to the invention, wherein the propylene homo or random copolymer matrix phase (A) is prepared first and the ethylene-propylene copolymer rubber phase (B) is prepared second in the presence of the first product. The heterophasic polypropylene composition is prepared third in the presence of the first and second product. The resulting powder optionally will be compounded under conventional conditions.

It is preferred that the propylene homo or random copolymer matrix (A) is produced in one or more polymerisation stages comprising slurry or gas phase reactors or a combination thereof and is afterwards transferred to at least one subsequent polymerisation stage comprising at least one gas phase reactor in which the ethylene-propylene rubber phase (B) is produced in the presence of component (A).

In other words, the process can comprise a slurry reactor and two gas phase reactors in a series (slurry/gpr/gpr), or two slurry reactors and one gas phase reactor in a series (slurry/slurry/gpr).

The slurry reactor(s) preferably is/are loop reactor(s). Thus, the reactor configurations preferably are loop/gpr/gpr or loop/loop/gpr configurations. c) Prepolymerisation and general options

Optionally, the first polymerisation stage includes a pre-polymerisation step in a manner known in the field which precedes the steps of the first polymerisation stage (a). A pre-polymerisation step as a matter of definition shall be part of the first polymerisation stage. Usually the prepolymerization will not take place in the reactor used for producing the first material but usually will take place in a reactor preceding the reactor used for producing the first material.

In a first embodiment the reaction conditions are as follows:

The first polymerisation stage (I) is preferably carried out in a slurry reactor at a temperature of 70 to 95 °C and a pressure of 50 to 60 barg. The second polymerisation (II) stage preferably is carried out in a gas phase reactor at a temperature of 80 to 95 °C and a pressure of 20 to 35 barg. The third polymerisation stage (III) preferably is carried out in a gas phase reactor at a temperature of 60 to 90 °C and a pressure of 14 to 22 barg.

In a second embodiment the reaction conditions are as follows:

The first polymerisation stage (I) is preferably carried out in a slurry reactor at a temperature of 60 to 85 °C and a pressure of 30 to 40 barg. The second polymerisation stage (II) is preferably carried out in a slurry reactor at a temperature of 60 to 85 °C and a pressure of 30 to 40 barg. The third polymerisation stage (III) is preferably carried out in a gas phase reactor at a temperature of 60 to 90 °C and a pressure of 7 to 5 barg.

For both embodiments the pre-polymerisation may be carried out in the reactor used for producing the first material at different temperatures and pressures or the pre-polymerisation may be carried out in a separate reactor preceding the reactor used for producing the first material.

The process according to the present invention is preferably a continuous process. d) First embodiment

Preferably, in the process for producing the heterophasic propylene copolymer in a sequence of a first polymerisation stage (I) comprising a slurry (loop) and second and third polymerisation stages (II) and (III) each comprising a gas phase reactor as defined above the conditions for the first polymerisation stage (I) may be as follows:

- the temperature is within the range of 45 °C to 115 °C, preferably between 65 °C and 105 °C, most preferably 60 to 90 °C, the pressure is within the range of 20 barg to 80 barg, preferably between 40 barg to 70 barg, most preferably between 50 to 60 barg, hydrogen is added for controlling the molar mass in a manner known per se, more preferably the H2/C3 ratio is in the range of 0.7 to 4.5 mol/kmol, more preferably 2.0 to 3.0 mol/kmol.

Subsequently, the reaction mixture from the first polymerisation stage (I) is transferred to the second polymerisation stage (II).

Preferably the split is adapted such that 35 to 65 wt.-%, more preferably 40 to 60 wt.-% and most preferably 45 to 55 wt.-% of the composition produced in the first and second reaction stage (together) is produced in the first reaction stage (I).

The conditions in stage (II) when carried out in a gas phase reactor are preferably as follows:

the temperature is within the range of 60 °C to 140 °C, preferably between 70 °C and 1 10 °C, and most preferably between 80 to 95°C,

the pressure is within the range of 5 barg to 50 barg, preferably between 15 barg to 35 barg, and most preferably between 20 to 35 barg,

hydrogen can be added for controlling the molar mass in a manner known per se, more preferably the H2 C3 ratio is in the range of 25 to 1 10 mol/kmol, more preferably 25 to 60 mol/kmol.

Still subsequently, the reaction mixture from the second polymerisation stage (II) is transferred to the third polymerisation stage (III).

The conditions in stage (III) when carried out in a gas phase reactor are preferably as follows:

the temperature is within the range of 40 °C to 00 °C, preferably between 55 °C and 75 °C, most preferably between 60 and 90 °C, the pressure is within the range of 2 barg to 50 barg, preferably between 5 barg to 25 barg, most preferably between 14 to 22 barg, hydrogen is added for controlling the molar mass in a manner known per se. More preferably the H2/C3 ratio is in the range of 40 to 85 mol/kmol,

the C2/C3 feed ratio is preferably in the range of 650 to 1000 mol/kmol, more preferably 680 to 780 mol/kmol.

Preferably 4.0 to 18.0 wt.-%, more preferably 5.0 to 15.0 wt.-% and most preferably 5.0 to 14.5 wt.-% of the final composition (i.e. all stages) is produced in the third reaction stage. e) Second embodiment

In the second embodiment in the process for producing the heterophasic propylene copolymer according to the present invention using a sequence of a first and second polymerisation stage carried out in a loop reactor and a third polymerisation stage carried out in a gas phase reactor as described above, the preferred conditions are as follows:

in the first polymerisation stage (I):

the temperature is within the range of 45 °C to 1 15 °C, preferably between 65 °C and 105 °C, most preferably 60 to 85 °C,

the pressure is within the range of 10 barg to 70 barg, preferably between 20 barg to 60 barg, most preferably between 30 to 40 barg, hydrogen can be added for controlling the molar mass in a manner known per se. Preferably hydrogen is used to adapt the MFR2 (of the intermediate resulting from this stage) to a range of 0.8 to 8.0 g/10min.

Subsequently, the reaction mixture from the first polymerisation stage (I) is transferred to the second polymerisation stage (II) being again carried out in a loop reactor. The split is preferably adapted to the identical ranges as disclosed for the first embodiments. Reference is made to the aforesaid.

The conditions in stage (II) are preferably as follows:

the temperature is within the range of 35 °C to 140 °C, preferably between 55 °C and 1 10 °C, and most preferably between 60 to 85 °C, the pressure is within the range of 10 barg to 70 barg, preferably between 20 barg to 60 barg, and most preferably between 30 to 40 barg,

hydrogen can be added for controlling the molar mass in a manner known per se. Preferably hydrogen is used to adapt the MFR2 (of the intermediate resulting from this stage) to a range of 6.0 to 9.0 g/10min.

Still subsequently, the reaction mixture from the second polymerisation stage (II) is transferred to the third polymerisation stage (III) carried out in a gas phase reactor.

The conditions in stage (III) are preferably as follows:

the temperature is within the range of 40 °C to 100 °C, preferably between 55 X and 95 °C, most preferably between 60 and 90 °C, the pressure is within the range of 2 barg to 50 barg, preferably between 5 barg to 25 barg, most preferably between 7 to 15 barg, hydrogen can be added for controlling the molar mass in a manner known per se. Preferably hydrogen is used to adapt the MFR2 of the final polymer to a range of 4.0 to 8.0 g/10min, more preferably of 4.0 to 7.0 g/10 min, even more preferably of 4.0 to 6.5 g/10 min and most preferably of 4.0 to 6.0 g/10 min.

the C2/C3 (mol/kmol) feed ratio is preferably in the range of 650 to 1000, more preferably 680 to 780.

Preferably 4.0 to 18.0 wt.-%, more preferably 5.0 to 15.0 wt.-% and most preferably 5.0 to 14.5 wt.-% of the final composition (i.e. all stages) is produced in the third reaction stage (III).

The residence time can vary in the polymerisation stages. The residence time in the polymerisation stage carried out in a slurry reactor, preferably a loop reactor typically is in the range 0.5 to 5 hours and mostly 30 to 40 min. The residence time in the reaction stage carried out in the gas phase reactor will generally be 1 min to 8 hours. The residence times required will depend on the catalyst system and can be figured out by persons skilled in the art via routine experimentation. In a further embodiment, the matrix (A) and the ethylene-propylene copolymer rubber component (B) can be polymerised separately and compounded by melt-mixing. However, this embodiment is not preferred.

Preferably, the heterophasic polypropylene composition is produced according to any of the above embodiments of the process. Thus, the heterophasic polypropylene composition of the present invention preferably is an in-situ blend. f) Compounding

The composition is preferably produced in a process comprising a compounding step, wherein the powder obtained from the third reaction stage (III) is extruded in an extruder and then pelletized to polymer pellets in a manner know in the art. Additive(s), filler(s), nucleating agent(s) and/or modifier(s) may be added during this extrusion stage, or in a separate compounding step.

The present invention further relates to an article comprising more preferably consisting of the heterophasic polypropylene composition or the filled heterophasic polypropylene composition according to the present invention.

In one embodiment, the article preferably is a moulded article, preferably an injection moulded or blow moulded article.

In another preferred embodiment, the article preferably is a part of a rain water management system, such as an infiltration system or a stormwater reservoir.

In another preferred embodiment, the article is an injection moulded pipe, fitting or manhole.

In another preferred embodiment, the article is an extruded pipe.

Furthermore, the present invention also pertains to infiltration boxes comprising and preferably consisting of the heterophasic polypropylene composition or the filled heterophasic polypropylene composition according to the present invention. Still further, the present invention relates to the use of the heterophasic polypropylene composition according to the invention for producing articles, more preferably articles as listed above.

In the following, the present invention is described by way of examples.

Examples:

1. Methods a) Melt Flow Rate

The melt flow rate (MFR) is determined according to ISO 1 133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg. b) Xylene Soluble Fraction

The xylene soluble fraction (XCS) as defined and described in the present invention is determined as follows: 2.0 g of the polymer were dissolved in 250 ml p-xylene at 135 °C under agitation. After 30 minutes, the solution was allowed to cool for 15 minutes at ambient temperature and then allowed to settle for 30 minutes at 25 ± 0.5 °C. The solution was filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml vessel was evaporated in nitrogen flow and the residue dried under vacuum at 90 °C until constant weight is reached. The xylene soluble fraction (percent) can then be determined as follows:

XCS% = (100 x nri! X v0)/(m0 x i) (1) wherein mo designates the initial polymer amount (grams), mi defines the weight of residue (grams), v0 defines the initial volume (milliliter) and v-i defines the volume of the analysed sample (milliliter). The fraction insoluble in p-xylene at 25 °C (XCU) is then equal to 100% - XCS%. c) Intrinsic Viscosity

The intrinsic viscosity (IV) value increases with the molecular weight of a polymer. The intrinsic viscosity of the XCU and the XCS fraction is measured in decalin at 135 °C according to DIN EN ISO 1628-1 and -3. d) Melting and crystallisation temperature

The melting and crystallisation temperature Tm and Tc are determined according to ISO 1 1357-1 , -2 and -3 with a TA-lnstruments 2920 Dual-Cell with RSC refrigeration apparatus and data station. A heating and cooling rate of 10 "C/min is applied in a heat / cool / heat cycle between +23 and +210 °C, the crystallisation temperature Tc being determined in the cooling step and the Tm melting temperature being determined in the second heating step. e) Melting and crystallisation heat

The heat of melting and heat of crystallisation HM and He are determined by differential scanning calorimetry (DSC) according to ISO 1 1357-1 , -2, and -3 with a TA-lnstruments 2920 Dual-Cell with RSC refrigeration apparatus and data station. f) Comonomer content

Quantitative Fourier transform infrared (FTIR) spectroscopy was used to quantify the amount of comonomer. Calibration was achieved by correlation to comonomer contents determined by quantitative nuclear magnetic resonance (NMR) spectroscopy.

The calibration procedure based on results obtained from quantitative 13C- NMR spectroscopy was undertaken in the conventional manner well documented in the literature.

The amount of comonomer (N) was determined as weight percent (wt.-%) via:

N = ki (A / R) + k2 (2) wherein A is the maximum absorbance defined of the comonomer band, R the maximum absorbance defined as peak height of the reference peak and with k-i and k2 the linear constants obtained by calibration. The band used for ethylene content quantification is selected depending if the ethylene content is random (730 cm"1) or block-like (720 cm"1). The absorbance at 4324 cm"1 was used as a reference band. g) Charpy Notched Impact Strength (NIS)

Charpy impact strength was determined according to ISO 179-1 eA:2000 on V-notched samples of 80x10x4 mm3 at 23 °C (Charpy impact strength (23 °C)) and -20 °C (Charpy impact strength (-20 °C)). The test specimens were prepared by injection moulding using an IM V 60 TECH machinery in line with ISO 1872-2. The melting temperature was 200 °C and the moulding temperature was 40 °C. h) Tensile Modulus

Mechanical properties were determined according to ISO 527-2. Injection moulded specimens of type 1A were used, which were prepared according to ISO 1872-2.

Tensile modulus (in MPa) was determined according to ISO 527-2. The measurement was conducted at 23 °C temperature with an elongation rate of 1 mm/min. i) Fiexural Modulus

The fiexural modulus was determined according to ISO 178 at a test speed of 2 mm/min and a force of 100 N, whereby the length of the span between the supports was 64 mm, on test specimens having a dimension of 80x10x4 mm3 (length x width x thickness) prepared by injection moulding according to EN ISO 1873-2. j) Average aspect ratio of filler

The average aspect ratio has been determined by recording transmission electron microscopy (TEM) images of the pure inorganic filler prepared onto film-coated TEM grids from an aqueous suspension by rotating the sample in 1 ° intervals from -75° to +75°, e.g. with JEOL JEM-2100 microscope, and reconstructing the three dimensional structure (e.g. with the JEOL TEMography™ software). 100 particles were measured and the average calculated. The aspect ratio of a particle is the ratio of the longest and shortest particle radii that pass through the geometric centre of the particle.

In case of anisotropy in one dimension (fiber-like) or two dimensions (platelet-like) structures the geometric centre equals the centre of gravity of the particle.

Rheological parameters The characterisation of polymer melts by dynamic shear measurements complies with ISO standards 6721 -1 and 6721 -10. The measurements were performed on an Anton Paar MCR501 stress controlled rotational rheometer, equipped with a 25 mm parallel plate geometry. Measurements were undertaken on compression moulded plates, using nitrogen atmosphere and setting a strain within the linear viscoelastic regime. The plates were prepared by compression moulding at 200°C with a holding time of 60 seconds

The oscillatory shear tests were done at 200 °C applying a frequency range between 0.01 and 600 rad/s and setting a gap of 1 .3 mm. In a dynamic shear experiment the probe is subjected to a homogeneous deformation at a sinusoidal varying shear strain or shear stress (strain and stress controlled mode, respectively). On a controlled strain experiment, the probe is subjected to a sinusoidal strain that can be expressed by

y(t) = Yo sin( >t) (3)

If the applied strain is within the linear viscoelastic regime, the resulting sinusoidal stress response can be given by

σ( = σ0 sin (tut + δ) (4) where σ0 and y0 are the stress and strain amplitudes, respectively; ω is the angular frequency; δ is the phase shift (loss angle between applied strain and stress response); t is the time.

Dynamic test results are typically expressed by means of several different Theological functions, namely the shear storage modulus G', the shear loss modulus, G", the complex shear modulus, G*, the complex shear viscosity, η*, the dynamic shear viscosity, η' and the out-of-phase component of the complex shear viscosity η" which can be expressed as follows:

G' = ^cos5 [Pa] (5) C = ^ sinS [Pa] (6)

Yo

G' + IG" [Pa] (7) η,' - ϊη" [Pa.s] (8)

- [Pa.s] (9)

- [Pa.s] (10) The values of storage modulus (G'), loss modulus (G"), complex modulus (G*) and complex viscosity (η*) were obtained as a function of frequency (ω). Thereby, e.g. η*30ο rad/s (eta*3oo rad/s) is used as abbreviation for the complex viscosity at the frequency of 300 rad/s and r o.os rad/s (eta*0.os rad/s) is used as abbreviation for the complex viscosity at the frequency of 0.05 rad/s.

The loss factor tangent tan or tan (delta) is defined as the ratio of the loss modulus (G") and the storage modulus (G') at a given frequency. Thereby, e.g. tan0.05 is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G') at 0.05 rad/s and tan30o is used as abbreviation for the ratio of the loss modulus (G") and the storage modulus (G') at 300 rad/s.

The elasticity balance tan0 05/tan3oo is defined as the ratio of the loss tangent tano.os and the loss tangent tan3oo-

The polydispersity index, PI, is defined by equation 1 1 .

P/ = ^C^) ' "COP = ω for dC = G") (1 1 ) where, OJCOP is the cross-over angular frequency, determined as the angular frequency for which the storage modulus, G' equals the loss modulus, G".

The values are determined by means of a single point interpolation procedure, as defined by Rheoplus software. In situations for which a given G* value is not experimentally reached, the value is determined by means of an extrapolation , using the same procedure as before. In both cases (interpolation or extrapolation), the option from Rheoplus "- Interpolate y-values to x-values from parameter" and the "logarithmic interpolation type" were applied.

References (incorporated by reference herewith):

[1 ] Rheological characterization of polyethylene fractions" Heino, E.L. , Lehtinen, A., Tanner J., Seppala, J. , Neste Oy, Porvoo, Finland, Theor. Appl. Rheol. , Proc. Int. Congr. Rheol, 1 1th (1992), 1 , 360- 362

[2] The influence of molecular structure on some rheological properties of polyethylene", Heino, E.L. , Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).

Definition of terms relating to the non-ultimate mechanical properties of polymers, Pure & Appl. Chem., Vol. 70, No. 3, pp. 701- 754, 1998.

2. Compositions: a) Comparative Examples (CE2-4):

Comparative Example CE2 is the commercially available product BD950MO (Borealis Polyolefine GmbH, Austria) being a heterophasic copolymer with an MFR2 of 7.0 g/10min, an XCS content of 13 wt.-%

Comparative example CE3 commercially available product BC250MO (Borealis Polyolefine GmbH, Austria) being a heterophasic copolymer with an MFR2 of 4 g/10min, an XCS content of 21 wt.-%

Comparative example CE4 has been prepared according to Example Ref 4 of EP 1 724 303 A1 being a heterophasic copolymer with an MFR2 of 0.3 g/10min, an XCS content of 14 wt.-%. b) Inventive Examples (IE1-9) and Comparative Example (CE1 ):

The catalyst used for the Inventive Examples IE1 -IE9 is a high yield MgCI2 supported Ziegler-Natta catalyst has been prepared according to Example 1 of EP 1 028 985. A prepolymer was produced using this catalyst at a temperature of 30°C and a pressure of 55 barg. The polymerisation was continued in a loop reactor. The second and the third polymerisation stage was performed in a gas phase reactor.

The powder was further melt homogenised and pelletized using a Coperion ZSK57 co-rotating twin screw extruder with screw diameter 57 mm and L/D 22. Screw speed was 200 rpm and barrel temperature 200-220 °C.

In IE1 -9 and CE1 , the following additives were added during the melt homogenisation step:

9000 ppm talc (TALC HM2 supplied by Imifabi S.P.A), 2200 ppm ADK STAB AO-60 (supplied by Adeka Corporation), 1900 ppm Songnox DSTPD (supplied by Songwon), 1600 ppm ADK-STAB 2112 RG (supplied by Adeka Corporation) and calcium stearate 400 ppm (CEASIT-AV/T, supplied by Baerlocher).

In IE7a, the following additives were added during the melt homogenisation step: 2200 ppm ADK STAB AO-60 (supplied by Adeka Corporation), 1900 ppm Songnox DSTPD (supplied by Songwon), 1600 ppm ADK-STAB 2112 RG (supplied by Adeka Corporation) and calcium stearate 400 ppm {CEASIT- AV/T, supplied by Baerlocher). c) IE10

IE 10 was produced by adding 20% talc (TALC HM2 supplied by Imifabi S.P.A.) to the polymer powder. In the same compounding step 2200 ppm ADK STAB AO-60 (supplied by Adeka Corporation), 1600 ppm ADK-STAB 2112 RG (supplied by Adeka Corporation) and calcium stearate 400 ppm (CEASIT-AV/T, supplied by Baerlocher) were added. Compounding was done on a Prism TSE 24 twin screw compounder with screw diameter of 24 mm and UD of 40 under standard conditions.

Table 1 : Properties and process data of Inventive and Comparative Examples.

Figure imgf000034_0001
C000/H0£d3/13d ΪΖ9ΐ9ΐ/Π0Ζ OAV The properties of the inventive examples and the comparative example are compared in Table 3. It can be seen that the inventive examples show clear advantages both in flexural modulus, NIS and MFR2.

*Examples IE7 and IE7a are the same compositions with the difference that IE7a does not include any talc.

**Talc in the amounts of below 1 wt.-% contributes to the nucleation.

***Processability is ranked ++, if the MFR value is above 4.5 g/10 min, +, if above 3.0 g/10 min, o, if above 2.5 g/10 min, -, if below 2.5 g/10 min, and --, if far below 2.5 g/10 min.

****lmpact is ranked ++, if the NIS (23 °C) value is above 7.0 J/m2, +, if above 6.0 J/m2, o, if above 5.5 J/m2, -, if below 5.5 J/m2, and — , if far below 5.5 J/m2.

*****Stiffness is ranked ++, if the flexural modulus value is above 1700 Pa, +, if above 1625 MPa, o, if above 1500 MPa, -, if below 1500 MPa, and --, if far below 1500 MPa.

ND: not determined

Claims

Claims
Heterophasic polypropylene composition comprising
a propylene homo- or random copolymer matrix phase (A), and an ethylene-propylene copolymer rubber phase (B) dispersed within the matrix phase,
the heterophasic polypropylene composition including
a fraction soluble in p-xylene at 25°C (XCS fraction) which is present in the resin in an amount of 4 to 14 wt.-%, and
a fraction insoluble in p-xylene at 25 °C (XCU fraction) which is present in the resin in an amount of 86 to 96 wt.-%,
wherein the heterophasic polypropylene composition has an MFR2, determined according to ISO 1 133 at 230 °C and under a load of 2.16 kg, of 4.0 to 8.0 g/10 min; and
wherein the heterophasic polypropylene composition has a flexural modulus higher than 1500 MPa measured on an injection moulded specimen with the dimension 80x10x4 mm3 according to ISO 178; and
wherein the heterophasic polypropylene composition has a content of monomer units derived from ethylene of 2.0 to 7.0 wt.- %.
The heterophasic polypropylene composition according to the claim 1 , wherein the composition optionally comprises 50 ppm to 1 .5 wt.-%, more preferably 100 ppm to 1 .3 wt.-%, and most preferably 0.1 to 1.2 wt.-% of an nucleating agent (F) with respect to the total weight of the heterophasic composition.
The heterophase polypropylene composition according to claim 2, wherein the nucleating agent (F) is talc and/or at least one vinyl cycloalkane polymer.
The heterophasic polypropylene composition according to any of the preceding claims, wherein the additives (E) content is below 1 .0 wt.-%, preferably of 0.1 to 0.8 wt.-%, and most preferably of
0.2 to 0.7 wt.-% with respect to the total weight of the heterophasic composition.
The heterophasic polypropylene composition according to any of the preceding claims, wherein the XCS fraction has a content of monomer units derived from ethylene of 25 to 55, more preferably of 30 to 50, and most preferably of 35 to 45 wt.-%.
The heterophasic polypropylene composition according to any of the preceding claims wherein the XCS fraction has an intrinsic viscosity of 3.5 to 6.0, more preferably of 4.0 to 5.8, and most preferably of 4.4 to 5.5 dl/g measured in decalin at 135°C according to DIN EN ISO 1628-1 and -3.
The heterophasic polypropylene composition according to any of the preceding claims wherein the heterophasic polypropylene composition has a flexural modulus of higher than 1500 MPa, preferably higher than 1625 MPa, even more preferably higher than 1650 MPa, and most preferably of higher than 1700 MPa, determined according to ISO 178.
The heterophasic polypropylene composition according to any of the preceding claims, wherein the heterophasic polypropylene composition has a content of monomer units derived from ethylene of 3.0 to 6.5, and preferably of 4.0 to 5.5 wt.-%.
The heterophasic polypropylene composition according to any of the preceding claims wherein the heterophasic polypropylene composition has a heat of melting, HM, of 85 to 125, preferably of 90 to 120, and more preferably of 95 to 1 16 J/g measured by differential scanning calorimetry (DSC) according to ISO 1 1357-1 , -2, and -3.
The heterophasic polypropylene composition according to any of the preceding claims wherein the heterophasic polypropylene composition has a heat of crystallization, He, of 80 to 120, preferably of 85 to 1 15, and more preferably of 90 to 1 1 1 J/g measured by differential scanning calorimetry (DSC) according to ISO 1 1357-1 , -2, and -3.
1 1. The heterophasic polypropylene composition according to any of the preceding claims wherein the heterophasic polypropylene composition has a crystallization temperature, Tc, of 1 18 to 135, preferably 128 to 132, and more preferably 129 to 131 °C measured according to ISO 1 1357-1 , -2 and -3.
12. The heterophasic polypropylene composition according to any of the preceding claims wherein the heterophasic polypropylene composition has a polydispersity index, PI, measured at 200°C of 2.5 to 6.0, preferably of 2.8 to 5.0, and more preferably of 3.0 to 4.2 Pa-1.
13. A filled heterophasic polypropylene composition consisting of the polypropylene composition according to any of claims 1 to 12 and a mineral, inorganic filler (C) in an amount of 5 to 55 wt.-%, preferably 15 to 45 wt.-%, and most preferably 20to 40 wt.-% with respect to the total weight of the filled heterophasic polypropylene composition.
14. The filled heterophasic polypropylene composition according to claim 13, wherein the mineral inorganic filler (C) is talc.
15. The filled heterophasic polypropylene composition according to claims 13 or 14, wherein the filled heterophasic polypropylene has a flexural modulus of higher than 2500 MPa, determined according to ISO 178.
16. A process for producing the heterophasic polypropylene composition according to any of the preceding claims in the presence of a Ziegler-Natta catalytic system modified with vinylcyclohexane comprising a cocatalyst, wherein the process comprises
a) production of a first material in a first polymerisation stage (I), having an MFR2 (2.16 kg, 230 °C) of 0.5 to 8 g/10 min, further having a XCS content of 0.5 to 2 wt.-%, wherein the first polymerisation stage (I) includes a slurry reactor and the process is run at a temperature of 70 to 95 °C and a pressure of 50 to 60 barg; b. transferring said first material in a second polymerisation stage (II);
c. further producing a second material,
wherein the second polymerisation stage (II) includes a gas phase reactor and the process is run at a temperature of 80 to 95 °C and a pressure of 20 to 35 barg;
d. transferring the mixture of said first and second materials having a MFR2 of 6 to 8 g/10 min in a third polymerisation stage (III),
wherein the third polymerisation stage (III) includes a gas phase reactor and the process is run at a temperature of 60 to 90 °C and a pressure of 14 to 22 barg;
e. optionally compounding the reaction product of the third polymerisation stage (III) with additive(s), optionally nucleating agent(s), optionally modifier(s) and/or optionally mineral inorganic filler(s).
Article comprising the heterophasic polypropylene composition according to any of claims 1 to 12 or the filled heterophasic polypropylene composition according to any of claims 13 to 15.
The article according to claim 17, whereby the article is an extruded or injection moulded pipe , a fitting, a manhole, or a part of a rain water management system.
PCT/EP2014/000388 2013-04-05 2014-02-12 High stiffness polypropylene compositions WO2014161621A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13001743.7A EP2787034A1 (en) 2013-04-05 2013-04-05 High stiffness polypropylene compositions
EP13001743.7 2013-04-05

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CN201480003021.7A CN104781336B (en) 2013-04-05 2014-02-12 The polypropene composition of high rigidity
AU2014247358A AU2014247358B2 (en) 2013-04-05 2014-02-12 High stiffness polypropylene compositions
PL14705031T PL2981575T3 (en) 2013-04-05 2014-02-12 High stiffness polypropylene compositions
US14/437,529 US20150299442A1 (en) 2013-04-05 2014-02-12 High stiffness polypropylene compositions
EP14705031.4A EP2981575B1 (en) 2013-04-05 2014-02-12 High stiffness polypropylene compositions

Publications (1)

Publication Number Publication Date
WO2014161621A1 true WO2014161621A1 (en) 2014-10-09

Family

ID=48128044

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/000388 WO2014161621A1 (en) 2013-04-05 2014-02-12 High stiffness polypropylene compositions

Country Status (7)

Country Link
US (1) US20150299442A1 (en)
EP (2) EP2787034A1 (en)
CN (1) CN104781336B (en)
AU (1) AU2014247358B2 (en)
HU (1) HUE034319T2 (en)
PL (1) PL2981575T3 (en)
WO (1) WO2014161621A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10266671B2 (en) * 2015-07-08 2019-04-23 Borealis Ag Tube made of a heterophasic polypropylene composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR201808436T4 (en) * 2013-04-22 2018-07-23 Abu Dhabi Polymers Co Ltd Borouge polypropylene compositions having improved impact resistance for pipe applications.
EP3227382A1 (en) * 2014-12-02 2017-10-11 SABIC Global Technologies B.V. Polypropylene composition comprising nucleating agent
EP3357964A1 (en) * 2017-02-03 2018-08-08 Borealis AG Use of a polymer composition for the production of articles with improved paintability and surface appearance
WO2019121599A1 (en) * 2017-12-20 2019-06-27 Borealis Ag Heterophasic polypropylene composition

Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347160A (en) 1980-06-27 1982-08-31 Stauffer Chemical Company Titanium halide catalyst system
US4382019A (en) 1981-09-10 1983-05-03 Stauffer Chemical Company Purified catalyst support
US4435550A (en) 1981-03-19 1984-03-06 Ube Industries, Ltd. Method for polymerizing α-olefin
US4465782A (en) 1981-08-07 1984-08-14 Imperial Chemistry Industries PLC Supported transition metal composition
US4473660A (en) 1982-02-12 1984-09-25 Montedison S.P.A. Catalysts for the polymerization of olefins
US4530912A (en) 1981-06-04 1985-07-23 Chemplex Company Polymerization catalyst and method
US4560671A (en) 1983-07-01 1985-12-24 Union Carbide Corporation Olefin polymerization catalysts adapted for gas phase processes
WO1987007620A1 (en) 1986-06-09 1987-12-17 Neste Oy Procedure for manufacturing catalyst components for polymerizing olefines
EP0491566A2 (en) 1990-12-19 1992-06-24 Borealis A/S A method for the modification of catalysts intended for the polymerization of olefins
WO1992012182A1 (en) 1990-12-28 1992-07-23 Neste Oy Multi-stage process for producing polyethylene
WO1992019659A1 (en) 1991-05-09 1992-11-12 Neste Oy A large-pore polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester
WO1992019653A1 (en) 1991-05-09 1992-11-12 Neste Oy A procatalyst for polymerization of olefins containing a trans-esterification product of a lower alcohol and a phthalic acid ester
WO1992019658A1 (en) 1991-05-09 1992-11-12 Neste Oy Coarse grained polyolefin, production thereof and a procatalyst containing a transesterification product between a lower alcohol and dioctylphthalate used therefore
WO1992021705A1 (en) 1991-05-31 1992-12-10 Neste Oy Method for preparing solid carrier particles of equal size for polymerization catalyst using rotating atomizing means
WO1993011165A1 (en) 1991-11-29 1993-06-10 Neste Oy Preparation of a solid ziegler catalyst by using a multifunctional, pivoting, inclinable reactor and the equipment for this
WO1993011166A1 (en) 1991-11-29 1993-06-10 Neste Oy Method for the preparation of a particulate carrier for a polymerization catalyst
WO1993019100A1 (en) 1992-03-24 1993-09-30 Neste Oy A polymerization catalyst carrier prepared by spray crystallization
FI96615B (en) 1993-06-04 1996-04-15 Neste Oy The method of C4-C40 olefin polymerization or copolymerization with other olefins
WO1997036939A1 (en) 1996-03-29 1997-10-09 Borealis A/S A novel composition, its preparation and use
WO1998012234A1 (en) 1996-09-19 1998-03-26 Borealis Polymers Oy PROCESS FOR THE POLYMERIZATION OF α-OLEFINS, A CATALYST USED IN THE POLYMERIZATION AND ITS PREPARATION
WO1998058975A1 (en) 1997-06-24 1998-12-30 Borealis A/S Process and apparatus for preparing propylene homopolymers and copolymers
WO1999024479A1 (en) 1997-11-07 1999-05-20 Borealis A/S Novel propylene polymers and products thereof
WO1999024478A1 (en) 1997-11-07 1999-05-20 Borealis A/S Process for preparing polypropylene
WO1999033842A1 (en) 1997-12-23 1999-07-08 Borealis Technology Oy Product containing magnesium, halogen and alkoxy
EP0991719A1 (en) 1997-06-24 2000-04-12 Borealis A/S Heterophasic propylene copolymer and process for its preparation
WO2000068315A1 (en) 1999-05-07 2000-11-16 Borealis Technology Oy High-stiffness propylene polymers and a process for the preparation thereof
WO2004000899A1 (en) 2002-06-25 2003-12-31 Borealis Technology Oy Polyolefin with improved scratch resistance and process for producing the same
WO2004111095A1 (en) 2003-06-06 2004-12-23 Borealis Technology Oy Process for the catalytic polymerization of olefins, a reactor system, its use in the process, the polyolefins obtained and their use
EP1619217A1 (en) 2004-07-20 2006-01-25 Borealis Technology Oy Cable with thermoplastic insulation
EP1632529A1 (en) 2004-09-02 2006-03-08 Borealis Technology Oy A pressureless polymer pipe, a composition therefore, and a process for preparing it
EP1724303A1 (en) 2005-05-20 2006-11-22 Borealis Technology Oy Polypropylene of improved processability for production of pipes
EP2072576A1 (en) 2007-12-18 2009-06-24 Borealis Technology OY Cable layer of modified soft polypropylene
EP2145923A1 (en) * 2008-07-16 2010-01-20 Borealis AG Heterophasic polymer composition of high stiffness
EP2191955A1 (en) * 2008-11-28 2010-06-02 Borealis AG Process for butt welding of polypropylene
WO2011117103A1 (en) 2010-03-22 2011-09-29 Borealis Ag Heterophasic polypropylene with excellent creep performance

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200427763A (en) * 2003-04-03 2004-12-16 Basell Poliolefine Spa Impact resistant polyolefin compositions
BRPI0412935B1 (en) * 2003-08-05 2014-08-05 Basell Poliolefine Srl Articles prepared by extrusion, molding and combinations thereof and their production process, single or multilayer tubes and heterophasic polyolefin composition
DE602006012732D1 (en) * 2005-12-20 2010-04-15 Basell Poliolefine Srl El
AT529450T (en) * 2009-02-25 2011-11-15 Borealis Ag Multimodal polymer of propylene, composition and method for the production thereof
CN102361927B (en) * 2009-03-23 2013-10-16 巴塞尔聚烯烃意大利有限责任公司 Polyolefin masterbatch and composition suitable for injection molding
WO2011160946A1 (en) * 2010-06-23 2011-12-29 Basell Poliolefine Italia Srl Polyolefin composition for pipe systems and sheets
ES2650670T3 (en) * 2010-06-23 2018-01-19 Basell Poliolefine Italia S.R.L. Pipes and polyolefin composition for their manufacture

Patent Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347160A (en) 1980-06-27 1982-08-31 Stauffer Chemical Company Titanium halide catalyst system
US4435550A (en) 1981-03-19 1984-03-06 Ube Industries, Ltd. Method for polymerizing α-olefin
US4530912A (en) 1981-06-04 1985-07-23 Chemplex Company Polymerization catalyst and method
US4465782A (en) 1981-08-07 1984-08-14 Imperial Chemistry Industries PLC Supported transition metal composition
US4382019A (en) 1981-09-10 1983-05-03 Stauffer Chemical Company Purified catalyst support
US4473660A (en) 1982-02-12 1984-09-25 Montedison S.P.A. Catalysts for the polymerization of olefins
US4560671A (en) 1983-07-01 1985-12-24 Union Carbide Corporation Olefin polymerization catalysts adapted for gas phase processes
WO1987007620A1 (en) 1986-06-09 1987-12-17 Neste Oy Procedure for manufacturing catalyst components for polymerizing olefines
EP0491566A2 (en) 1990-12-19 1992-06-24 Borealis A/S A method for the modification of catalysts intended for the polymerization of olefins
FI86866B (en) 1990-12-19 1992-07-15 Neste Oy Foerfarande Foer modifiering katalysatorer intended one of Foer polymerisation of olefins.
WO1992012182A1 (en) 1990-12-28 1992-07-23 Neste Oy Multi-stage process for producing polyethylene
FI88047B (en) 1991-05-09 1992-12-15 Neste Oy Pao Tvenne elektrondonorer baserad Katalysator Foer polymerisation of olefins
WO1992019653A1 (en) 1991-05-09 1992-11-12 Neste Oy A procatalyst for polymerization of olefins containing a trans-esterification product of a lower alcohol and a phthalic acid ester
WO1992019658A1 (en) 1991-05-09 1992-11-12 Neste Oy Coarse grained polyolefin, production thereof and a procatalyst containing a transesterification product between a lower alcohol and dioctylphthalate used therefore
WO1992019659A1 (en) 1991-05-09 1992-11-12 Neste Oy A large-pore polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester
FI88048B (en) 1991-05-09 1992-12-15 Neste Oy Grovkornig polyolefin, Dess framstaellningsmetod and an i metoden anvaend Katalysator
EP0591224A1 (en) 1991-05-09 1994-04-13 Borealis A/S A procatalyst for polymerization of olefins containing a trans-esterification product of a lower alcohol and a phthalic acid ester
WO1992021705A1 (en) 1991-05-31 1992-12-10 Neste Oy Method for preparing solid carrier particles of equal size for polymerization catalyst using rotating atomizing means
WO1993011165A1 (en) 1991-11-29 1993-06-10 Neste Oy Preparation of a solid ziegler catalyst by using a multifunctional, pivoting, inclinable reactor and the equipment for this
WO1993011166A1 (en) 1991-11-29 1993-06-10 Neste Oy Method for the preparation of a particulate carrier for a polymerization catalyst
WO1993019100A1 (en) 1992-03-24 1993-09-30 Neste Oy A polymerization catalyst carrier prepared by spray crystallization
FI96615B (en) 1993-06-04 1996-04-15 Neste Oy The method of C4-C40 olefin polymerization or copolymerization with other olefins
WO1997036939A1 (en) 1996-03-29 1997-10-09 Borealis A/S A novel composition, its preparation and use
WO1998012234A1 (en) 1996-09-19 1998-03-26 Borealis Polymers Oy PROCESS FOR THE POLYMERIZATION OF α-OLEFINS, A CATALYST USED IN THE POLYMERIZATION AND ITS PREPARATION
WO1998058975A1 (en) 1997-06-24 1998-12-30 Borealis A/S Process and apparatus for preparing propylene homopolymers and copolymers
EP0887379A1 (en) 1997-06-24 1998-12-30 Borealis A/S Process and apparatus for preparing propylene homopolymers and copolymers
EP0991719A1 (en) 1997-06-24 2000-04-12 Borealis A/S Heterophasic propylene copolymer and process for its preparation
WO1999024478A1 (en) 1997-11-07 1999-05-20 Borealis A/S Process for preparing polypropylene
WO1999024479A1 (en) 1997-11-07 1999-05-20 Borealis A/S Novel propylene polymers and products thereof
EP1028985A1 (en) 1997-11-07 2000-08-23 Borealis A/S Novel propylene polymers and products thereof
WO1999033842A1 (en) 1997-12-23 1999-07-08 Borealis Technology Oy Product containing magnesium, halogen and alkoxy
WO2000068315A1 (en) 1999-05-07 2000-11-16 Borealis Technology Oy High-stiffness propylene polymers and a process for the preparation thereof
WO2004000899A1 (en) 2002-06-25 2003-12-31 Borealis Technology Oy Polyolefin with improved scratch resistance and process for producing the same
WO2004111095A1 (en) 2003-06-06 2004-12-23 Borealis Technology Oy Process for the catalytic polymerization of olefins, a reactor system, its use in the process, the polyolefins obtained and their use
EP1619217A1 (en) 2004-07-20 2006-01-25 Borealis Technology Oy Cable with thermoplastic insulation
EP1632529A1 (en) 2004-09-02 2006-03-08 Borealis Technology Oy A pressureless polymer pipe, a composition therefore, and a process for preparing it
EP1724303A1 (en) 2005-05-20 2006-11-22 Borealis Technology Oy Polypropylene of improved processability for production of pipes
EP2072576A1 (en) 2007-12-18 2009-06-24 Borealis Technology OY Cable layer of modified soft polypropylene
EP2145923A1 (en) * 2008-07-16 2010-01-20 Borealis AG Heterophasic polymer composition of high stiffness
EP2191955A1 (en) * 2008-11-28 2010-06-02 Borealis AG Process for butt welding of polypropylene
WO2011117103A1 (en) 2010-03-22 2011-09-29 Borealis Ag Heterophasic polypropylene with excellent creep performance

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Definition of terms relating to the non-ultimate mechanical properties of polymers", PURE & APPL. CHEM., vol. 70, no. 3, 1998, pages 701 - 754
HEINO, E.L.: "The influence of molecular structure on some rheological properties of polyethylene", BOREALIS POLYMERS OY, PORVOO, FINLAND, ANNUAL TRANSACTIONS OF THE NORDIC RHEOLOGY SOCIETY, 1995
HEINO, E.L.; LEHTINEN, A.; TANNER J.; SEPPÄLÄ, J.: "Rheological characterization of polyethylene fractions", NESTE OY, PORVOO, FINLAND, THEOR. APPL. RHEOL., PROC. INT. CONGR. RHEOL, vol. 1, 1992, pages 360 - 362, XP008137571

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10266671B2 (en) * 2015-07-08 2019-04-23 Borealis Ag Tube made of a heterophasic polypropylene composition

Also Published As

Publication number Publication date
AU2014247358B2 (en) 2015-10-29
EP2787034A1 (en) 2014-10-08
HUE034319T2 (en) 2018-02-28
US20150299442A1 (en) 2015-10-22
PL2981575T3 (en) 2018-02-28
EP2981575A1 (en) 2016-02-10
EP2981575B1 (en) 2017-08-30
CN104781336A (en) 2015-07-15
AU2014247358A1 (en) 2015-05-21
CN104781336B (en) 2018-03-27

Similar Documents

Publication Publication Date Title
EP1963424B1 (en) Polypropylene composition comprising a propylene homopolymer component
EP2243803B1 (en) Tough composition for food applications
EP2283072B1 (en) High purity heterophasic propylene copolymers
US9382410B2 (en) Glass fiber composite of improved processability
US5409992A (en) Calenderable blends containing broad molecular weight distribution propylene polymer material
CN102947385B (en) Propylene polymer composition having superior hexane extractables/impact balance
KR101361432B1 (en) High flowable heterophasic polypropylene
ES2407640T3 (en) Low emission polymer composition
US9487648B2 (en) High flow polyolefin composition with low shrinkage and CLTE
AU2010217643B2 (en) Multimodal polymer of propylene, composition containing the same and a process for manufacturing the same
WO2009077034A1 (en) Heterophasic polypropylene with high impact properties
EP2601260A1 (en) Heterophasic propylene copolymer with excellent impact/stiffness balance
KR101495488B1 (en) High-flow fiber reinforced polypropylene composition
CN103025821B (en) Heterophasic polypropylene with excellent creep performance
ES2715385T3 (en) Composition of high flow polyolefin with high rigidity and toughness
EP2666818B1 (en) High flow polypropylene with excellent mechanical properties
EP2539398B2 (en) Random propylene copolymers for pipes
EP2638109A1 (en) Heterophasic propylene copolymers with improved stiffness/impact/flowability balance
US9074085B2 (en) Heterophasic polypropylene with high flowability and enhanced mechanical properties
CA2919171A1 (en) High flow polyolefin composition with high stiffness and toughness
WO2013026745A1 (en) Heterophasic system with improved surface properties
CN102066478B (en) Thermoplastic polyolefins with high flowability and excellent surface quality produced by a multistage process
AU2006328905B2 (en) Polypropylene composition comprising a propylene copolymer component
EP3105287B1 (en) Polypropylene composite
EP2902438B1 (en) High flow polyolefin composition with high stiffness and puncture resistance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14705031

Country of ref document: EP

Kind code of ref document: A1

REEP

Ref document number: 2014705031

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014705031

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14437529

Country of ref document: US

ENP Entry into the national phase in:

Ref document number: 2014247358

Country of ref document: AU

Date of ref document: 20140212

Kind code of ref document: A

NENP Non-entry into the national phase in:

Ref country code: DE